© 2016 The Royal Society of Chemistry.Herein we report the synthesis of a stimuli-responsive binuclear Au(i) complex based on the 1,5-bis(p-tolyl)-3,7-bis(pyridine-2-yl)-1,5-diaza-3,7-diphosphacyclooctane ligand, which is a novel template for the design of luminescent metal complexes. In the solid state, the complex obtained gives three different crystalline phases, which were characterized by XRD analysis. It was also found that the crystalline phases can be reversibly interconverted by recrystallization or solvent vapour treatment. The emission of these phases varies in the 500-535 nm range. Quite unexpectedly, the emission energy of these phases is mostly determined by the non-covalent interactions of the solvent molecules with the ligand environment, which have nearly no effect on the Au-Au interactions in the chromophoric centre. The complex obtained demonstrates thermo/solvatochromism to display greenish emission in a DCM matrix and blue emission in an acetone matrix at 77 K, in contrast to the blue emi